DE3715051A1 - PHOSPHATE-FREE DETERGENT BUILDER - Google Patents

Description

The invention relates to a phosphate-free Detergent builder.

It is known to be mixtures of zeolite A and a mixture from a homopolymeric and a copolymeric acrylic acid in Use detergent (see. DE-OS 34 44 960).

It is also known to use mixtures of polyacrylic acids different molecular weights in detergents used (cf. EP-OS 1 08 429).

The invention relates to a phosphate-free Detergent builder, consisting of a water-insoluble, for binding calcium ions and a silicate Mixture of two different acrylic acid polymers, the have a different viscosity number.

The mixture of the two different ones Acrylic acid polymers can preferably consist of two Homopolymers exist.

In another embodiment of the invention, the Mixture of the two acrylic acid polymers from one Homopolymer and a copolymer exist.

In a further embodiment of the invention, the Mixture of the two acrylic acid polymers from two different copolymers exist.

In a preferred embodiment of the invention the acrylic acid polymers have a viscosity number of 15 to 60, in particular between 20 and 35, and from 80 to 200, in particular between 90 and 120.

In a preferred embodiment of the invention can be as water-insoluble, capable of binding calcium ions Silicate a finely divided bound water containing synthetically produced, water-insoluble compound of general formula

(Kat _{2 / n} O) _x · Me₂O₃ · (SiO₂) _y (I),

in the cat use a cation exchangeable with calcium of the valence n , x is a number from 0.7 to 1.5, Me boron or aluminum and y is a number from 0.8 to 6. Aluminum silicates are particularly preferably used.

The aluminum silicates to be used can be amorphous or crystalline products, wherein of course also mixtures of amorphous and crystalline products and also semi-crystalline products can be used. The aluminum silicates can of course existing or synthetically manufactured products be, with the synthetically manufactured products are preferred. The production can e.g. B. by reaction of water-soluble silicates with water-soluble Aluminates take place in the presence of water. To this Purpose can be aqueous solutions of the starting materials mixed together or one in solid state present component with the other as aqueous Solution present component are implemented. Also through Mix the two, present in solid state Components are obtained in the presence of water desired aluminum silicates. Also from Al (OH) ₃, Al₂O₃ or SiO₂ can be reacted with alkali silicate or Produce aluminate solutions. The Production can also by other known methods respectively. In particular, the invention relates to Aluminum silicate, which is a three-dimensional Show space lattice structure.

The preferred, approximately in the range of 100 to 200 mg CaO / g AS mostly around 100 to 180 mg CaO / g AS Calcium binding capacity is found primarily in compounds the composition:

0.7 - 1.1 Na₂O · Al₂O₃ · 1.3 - 3.3 SiO₂

This empirical formula comprises two types of different ones Crystal structures (or their non-crystalline structures Intermediate products), which are also characterized by their empirical formulas differentiate. They are:

a) 0.7 - 1.1 Na₂O · Al₂O₃ · 1.3 - 2.4 SiO₂ b) 0.7 - 1.1 Na₂O · Al₂O₃ · 2.4 - 3.3 SiO₂

The different crystal structures are shown in the X-ray diffraction pattern.

The amorphous or in aqueous suspension crystalline aluminum silicate can be filtered separate from the remaining aqueous solution and at Temperatures of e.g. B. dry 50 to 400 ° C. Depending on the The product contains more or less drying conditions bound water.

Such high drying temperatures are generally not recommendable; expediently one does not go over 200 ° C if the aluminum silicate for use in Detergents and cleaning agents is provided. The However, aluminum silicates need to be manufactured for the preparation of a suspension according to the invention at all not to be dried; rather, it can - and it is particularly advantageous - one from the manufacture still damp aluminum silicate can be used. It can be however also at medium temperatures, for example at 80 to 200 ° C, until the adhering liquid is removed Water-dried aluminum silicates for preparation Use suspensions according to the invention.  

The particle size of the individual aluminum silicate particles can be different and z. B. in the range between 0.1 µ and 0.1 mm. This refers to the Primary particle size, d. that is, the size of the precipitate and optionally the subsequent crystallization resulting particles. Used with particular advantage aluminum silicates, which consist of at least 80% by weight Particles with a size of 10 to 0.01 μ, in particular of 8 to 0.1 µ exist.

These aluminum silicates preferably do not contain any Primary or secondary particles more with diameters above 45 µ. Secondary particles are particles that by agglomeration of the primary particles to larger Formations have arisen, referred to.

With regard to the agglomeration of the primary particles too Larger entities have used their Production of still moist aluminum silicates for production the suspensions according to the invention have been particularly successful since it has been found that when using this still wet products form secondary particles is practically completely prevented.

In a particularly preferred embodiment of the Invention is used as component A powdered zeolite Type A with a particularly defined particle spectrum used.

Such zeolite powder can according to DE-AS 24 47 021, 25 17 218, DE-OS 26 52 419, 26 51 420, 26 51 436, 26 51 437, 26 51 445,  26 51 485 can be produced. You then assign those there specified particle distribution curves.

In a particularly preferred embodiment, a Type A powdered zeolite can be used which that described in DE-OS 26 51 485 Has particle size distribution.

The resulting polymers can be used both as an acid and also as a salt or as a partially neutralized substance be used; metal ions are suitable as counterions as well as nitrogenous cations.

In the detergent builder according to the invention Acrylic acid polymers used are Homopolymers of acrylic acid or copolymers of Acrylic acid containing at least 50 mol% Acrylic acid. The copolymers can be used as further Monomers other ethylenically unsaturated mono- or Dicarboxylic acids with 3-8 C atoms contain such. B. Methacrylic acid, itaconic acid or maleic acid or their Anhydride. Before these monomers containing carboxyl groups the proportion in the copolymer can be up to 50%. In addition, the copolymers can contain no carboxyl groups ethylenically unsaturated monomers up to a proportion of Contain 20 mol%.

In particular, as monomers free of carboxyl groups, for example called acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid, Allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, Vinyl acetate, vinyl propionate, esters of acrylic acid or  Methacrylic acid with 1-8 carbon atoms in the alcohol residue, such as Methyl methacrylate, ethyl methacrylate, butyl methacrylate, Methyl acrylate, ethyl acrylate, butyl acrylate, Ethylhexyl acrylate, hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, dialkylaminoethyl (meth) acrylate, Vinyl glycol, allyl alcohol, ethylene, propylene, isobutylene, Methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, Styrene or butadiene.

The acrylic acid polymers are made by known processes produced.

Such processes are described, for example, in "Acrylic acid polymers ", M.L. Mitter in Encyclopedia of polymer science and technology, Vol. 1 Interscience Publishers, New York 1964.

The homopolymers or copolymers can be prepared by all customary free-radical polymerization processes. For example, the following are mentioned as production methods:
Solution polymerization, the monomers being dissolved in water or in another solvent or solvent mixture with any additions of low molecular weight organic and / or inorganic compounds.
Precipitation polymerization in solvents in which the monomers are at least partially soluble and the polymers are not soluble.
Emulsion polymerization and suspension polymerization in solvents in which the monomers are not soluble and the emulsions or suspensions are stabilized by adding low and / or high molecular weight substances.

The monomer concentration ranges between 5% and 70%, depending on the viscosity of the resulting polymer solution 25% to 50% is preferred.

Both thermally decomposable initiators Radical donors that have sufficient solubility in the possess the desired solvent or in the monomer, as well as multi-component redox initiators.

Radiation-induced polymerization can also be used used to prepare the acrylic acid polymers will.

The polymerization temperature is measured together with the The amount of initiator used to determine the molecular weight of the to control the desired polymer. It lies between 30 ° C and 180 ° C, it is advantageous to use them between Maintain 60 ° C and 120 ° C. Bring low temperatures mostly too high molecular weight polymers, too high Temperatures can cause polymer degradation and coloring.

The molecular weight can also be adjusted by suitable regulators such as Thio derivatives and low molecular weight alcohols can be controlled. A relative measure of the average molecular weight is Viscosity number (ml / g).

The polymer mixture according to the invention contains at least a homo- or copolymer (a) with viscosity number (VZ) between 15 and 60, preferably between 20 and 35, and a Homo- or copolymer (b) with VZ between 80 and 200, preferably between 90 and 120. The ratio a / b varies between 1/99 and 99/1, preferably between 25/75 and 75/25. The preparation according to the invention can be both  Mixing the separately prepared polymers as well be made in a single synthetic step by controlling the dosing time of the various Components, the reaction temperature and the Reaction time the polymers with different Molecular weight or different viscosity over time arise one after the other.

The polymer mixture or those produced in one step Polymers have the same physicochemical and application properties.

The viscosity number is a known quantity. Your The determination is described in the test specification DIN 53 727.

Based on the well-known DIN regulation, the Viscosity number of those used according to the invention various acrylic acid polymers as follows:

I. method

Aqueous polycarboxylic acid Na salt solution is (under Consideration of the solids content and at Polycarboxylic acids after weighing correction to polycarboxylic acid Na salt (determination of the acid number of an aqueous solution (2 g polymer in 100 cm³ 0.1 M of NaBr pH = 10.0) produced. The viscosity number of this solution is in an Ubbelohde viscometer capillary Oa at 25 ° C determined.  

II. Devices

Viscotimer (Schott)
Measuring stand (Schott)
Viscotimer frame made of V4A steel
Ubbelohde viscometer capillary Oa
Lauda see-through thermostat D40-SN
Evaluation can be carried out with the HP 97 S calculator
Arithmetic program

The viscosity number (ml / g) is a relative measure of that average molecular weight and for the average Degree of polymerization.

The viscosity number (VZ) (cm³ / g) is the relative change in viscosity divided by the concentration c (g / cm³) of the solution.

Instead of the dynamic viscosity of the polymer solution and the dynamic viscosity h _{o of} the solvent, the throughput times t of the measuring solution and t _o of the solvent are used in practice to determine the viscosity number (VZ) and are calculated using the following formulas:

The concentration c is specified at 2.0 g / 100 cm³, so it is a single-point measurement. The VZ is therefore only defined if the capillary, capillary constant, concentration, solvent and measuring temperature are specified.

The measured run-down times must be corrected by Δ t according to Hagenbach.

Relative viscosity: t / t _o

This dimensionless number represents the ratio of the efflux time of the polymer solution (t corr) and the solvent (t _o corr) represents, and is the basis for the calculation of VN.

Here, too, the result depends on the measurement conditions. In general, eta-rel should not exceed 2, otherwise a different polymer concentration or a different capillary must be selected.
The intrinsic viscosity and the average molecular weight M can be calculated from the VZ.

Calculation of the intrinsic viscosity η Calculation of the average weight average Molecular weight in PAS or POC HS Measuring principle

It is a time measurement. The throughput time t _{o of} the solvent (0.1 M aqueous NaBr pH = 10.0) is measured in an Ubbelohde capillary viscometer with the capillary Oa and at 25.0 ° C. This time measurement to 0.01 seconds takes place with the measuring stand AVS / ST, which is equipped with 2 light barriers.

The throughput time t of the measuring (polymer) solution is determined in the same viscometer.

The measuring solution contains 2.0 g (POC solids calculated on OS) per 100 cm³ in 0.1 M NaBr pH = 10.0.  

For these two throughput times, the Hagenbach correction (Δ t ; seconds) must be calculated, by which the times t and t _o must be corrected (Eq. 3; 4). From the corrected throughput times measured value t corr and blank value t _o corr and the concentration c (g / 100 cm³) the parameter for the average molecular weight becomes

- viscosity number = VZ (cm³ / g);

calculated (Eq. 8).

execution Measurement conditions

Capillary Oa
Measuring temperature 25 ° C ± 0.01 ° K
Solvent: 0.1 M NaBr aqueous pH = 10.0 ± 0.05
Polymer concentration of the measurement solution: 2,000 ± 0.02
Polycarboxylic acid
Na salt
Time measurement: to 0.01 seconds (light barrier)
Number of measurements: 3 (3 values are required for the computer program)

Solvent: 50 ml
0.1 M NaBr pH = 10.0

The Hagenbach correction is not carried out.  

Weigh the polymer solution

When weighing in for the measuring solution for VZ must

• 1. the solids content and
• 2. the type of polymer (whether the polymer is an acid = POC HS PAS, neutral = POC-AS or as Na salt = POC-OS PAS-N is present)

be taken into account.

Weighing at POC-HS and PAS-S

The solids content of the POC-HS or PAS * is according to AV 318.1 to determine.

The acid number of the POC-HS or PAS * is to be determined according to AV 319.1.
* P

0.393 = correction factor because polycarboxylic acid weighed in the measuring solution but 2% of polycarboxylic acid Na salt must be. SZ-F = solid acid number in mg KOH / g determined according to AV 319.1  

Weighing at POC-OS and PAS-N

already exists as a polycarboxylic acid sodium salt and will only corrected for solid. Also applies to type POC-AS!

Preparation of the measurement solution

B g of POC solution are placed in a 100 ml beaker
(Calculation of the exact sample weight for POC-HS (PAS-S) according to 6.2.1, for POC-AS according to 6.2.2, for POC-OS (PAS-N) according to 6.2.2)
weighed in.

After adding approx. 20 ml dist. H₂O and pipetting of 5 ml of 1 M NaBr solution is dissolved cold while stirring. With the Knick digital pH meter (electrode EA 121) is measured pH value (approx. 2-3 for HS pH, approx. 7-8 for OS pH), and sets the pH value of with stirring by adding NaOH 10.0 ± 0.05 a. 1 hour after the last NaOH addition the pH is checked again and corrected if necessary.

For weight calculation, point 6.2.2 for POC-OS, POC-AS or PAS-N (i.e. from polycarboxylic acid Na salts) is given in Program step 7 SZ-F: 0 on.  

The viscosity number is according to the formula

calculated.

c = concentration of the PAS-NA salt measurement solution in g / cm³ t = throughput time of the polymer solution t _o = throughput time of the binding value

The intrinsic viscosity η is calculated using the following formula:

D _SB = constant for PAS and POC equal to 0.15.
K _SB = 0.15

The weight average molecular weight leaves can be calculated as follows:

The detergent builder of the present invention has the following Advantages on:

Very good calcium binding capacity
Very good anti-disposition effect
Very good inhibition of heating rod incrustations
Very good inhibition of tissue incrustation

During the phosphate-free according to the invention Detergent builder, balanced in all four points, shows excellent advantages are the well-known Detergent builders only unbalanced in individual points advantageous.

Examples a) Determination of the viscosity number (VZ)

The VZ is measured using an Ubbelohde capillary viscometer measured with capillary Oa at 25 °. The is measured Lead time of a 2% (weight) polymer solution in 0.1 molar NaBr at pH 10. The pH is adjusted by adding discontinued by NaOH. The difference is called VZ between the lead time, the sample and that of the pure Solvent divided by the polymer concentration of the measured sample.

b) Examples for the preparation of the polymers

The parts specified below are understood as Parts by weight. The reactor can be thermostated, designed for a pressure up to 10 bar, provided with a stirrer and with supply lines for the various components.

Example 1

250 parts of deionized water are mixed with 2.6 parts 50% H₂O₂ submitted and brought to 90 ° C. 415 parts of acrylic acid and 11 parts are separated from one another dissolved in 720 parts of deionized water Sodium peroxodisulfate added at 90 ° C for 2 hours. This is followed by 1.5 hours of post-reaction time for the same Temperature. A polymer with VZ = 100 cm³ / g is formed.

Example 2

185 parts of deionized water are placed in and on Brought to 100 ° C. If the temperature remains constant  200 parts of acrylic acid and 16.7 parts in 100 for 2 hours Dissolve sodium peroxodisulfate in portions of deionized water fed separately from each other. It follows 1 hour Post-reaction at 100 ° C. A polymer is formed VZ = 24 cm³ / g.

Example 3

80 parts of deionized water are introduced. Under Nitrogen atmosphere becomes a pressure of 3.5 bar set and the reactor contents heated to 135 ° C. Under these conditions, 60 parts are deionized Water, 19 parts of 50% H₂O₂ and 80 parts of acrylic acid within 4 hours through separate lines added. This is followed by 2 hours of post-reaction, during the the temperature drops to 90 ° C. It arises Polymer with VZ = 14 cm³ / g.

c) Testing the detergent builder according to the invention in Detergents

The detergents are on a Telschig Spray mixer manufactured. The surfactants are together with the opt. Brightener sprayed hot. Then with Sikalon D, enzyme, beef soap, Powdered tallow soap and tallow alcohol.

For recipes, see table 1.

The washing tests are carried out on 3 Miele washing machines, W 763, alternating cyclically with a water hardness of approx. 20 ° dH and a washing temperature of 60 ° C in the cooking / color program performed over 25 washes.  

The ballast fabric consists of 3 kg of terry cloth Cotton fabric.

For each wash cycle, 150 g of washing powder are used for preliminary and Main wash dosed.

White towels (previously 2 × with 95 ° C prewashed) with sewn-on stains (approx. 22 × 15 cm). There are two on each towel Soiling is sewn alternately.

The following soiling was used:

EMPA standard ²)
WFK tea ¹)
WFK skin fat ¹)
EMPA red wine ²)
EMPA sulfur black ²)

¹) WFK = laundry research Krefeld (Germany) ²) EMPA = Federal Materials Testing Institute, St. Gallen (Switzerland)

Every second wash is used to harden the liquor each an approx. 22 × 15 cm strip with the following Soiling given:

EMPA standard
EMPA blood
EMPA tea
EMPA sulfur black

There are 2 ½ towels (approx. 550 g) with the Soiling used for a detergent and after the first wash colorimetrically matched. The Primary washing capacity is one wash per machine - a total of 3 primary washes - determined.

To determine the secondary washing power for each Detergent a strip of cotton and terry cloth washed and after 25 washes the incrustation values certainly.

Terrycloth and cotton: ashed for 1 h at 1000 ° C Towel: Ashes for 2 hours at 1000 ° C

The degree of graying was on cotton with green Strips (WFK) measured after the 10th and 25th wash.

The colorimetric sampling takes place on the Filter color measuring device RFC 3 (Zeiss). For evaluation, the Whiteness used according to Berger.

The evaluation takes place under statistical Points of view. To the measurement effort within reasonable limits hold (measuring area: 3 cm ⌀, measuring time: approx. 2 ′ per The following measuring points are taken.

Primary wash: 3 points per soiling, with 3 Repetitions, a total of 9 points.  Graying: 3 measuring points each

After checking for outliers (1) are mean values _i  and Standard deviationsS _i  determined (2). Significant Differences are determined by determining the LSD value (least significant difference) (3) found:

• a) same sample size n _i = const.
• b) unequal sample sizes n _i ≠ const. k = number of groups (here: 8) F _l ; n - k ; α = table value for the so-called "F test" (application: analysis of variance etc.); applied here at the 5% error level (α = 0.05) s ² _in is called "variance within the group" (mean value of the squared deviations of the individual values around the group mean values) and is calculated from the individual standard deviations s _i according to the following formula Group calculated (4).

The averages _i  are sorted by descending size and the mean differences based on the LSD criterion checked for significance. Non-significant differences are determined by underlining the mean values with a common line identified.

For the overall assessment of the primary detergent capacity, the Wilcoxon-Wilcox test (multiple mean comparisons based on rank numbers) (5). For every Soiling becomes one with regard to the 8 recipes Rank 1-8 (same means get one "medium" rank) and the individual ranks for every recipe added. The differences of these ranks are compared by tabulated values (5% level) examined for significance.

(1) Lothar Sachs, Applied Statistics, 4th edition, Springer-Verlag, 1973, pp. 219-221
(2) ibid., Pp. 57, 58
(3) ibid., P. 394; Tables on p. 116-124
(4) ibid., Pp. 63, 386-389
(5) ibid., Pp. 426-429

In primary washing ability (Tables 2 and 3) and except for Formulations 4 and 7 with the PAS VZ = 9 no differences noticeable. This is an indication of the well-known The fact that the main effect of PAS or polymers generally focused on improving the Detergent, in terms of secondary washing ability.

The graying (Table 4) shows a clear one Gradation in the range of effects of the PAS. Surprisingly it is found that polymer mixtures are significant achieve better degrees of whiteness than with the individual PAS, especially compared to the two commercially available Products (recipes 1 and 8). This behavior indicates clearly on synergistic effects, which only with the Mixtures take effect.

This behavior is also reflected in the Differences between the 10th and the 25th wash again. Mixtures of PAS show a clear withdrawal of the Whiteness levels, the individual PAS, however, a slight Decrease.

The mentioned synergism has a pronounced effect on the incrustation values. In particular, the mixture according to the invention of formulation 6 of 50 parts PAS VZ = 100 (example 1) and 50 parts PAS VZ = 24 (example 2) leads to a significant reduction in the incrustation values, particularly on tightly woven cotton fabric. The values with the PAS VZ = 9 are unexpectedly high (see recipe 4 and 7). This indicates a lower limit for the optimal VZ range for the low molecular weight PAS component in PAS mixtures.
Alkylbenzenesulfonate 3.5 alkyl sulfate, C₁₆ / C₁₈ 3.5 Na toluenesulfonate 0.8 tallow alcohol 5 EO 2.0 oxo alcohol 9 EO, C₁₃ / C₁₅ 2.0 tallow soap 2.0 beef soap 2.0 tallow alcohol 0.5 zeolite A26.3 Polymer *) 2.0 Na disilicate 6.0 Na perborate tetrahydrate 19.0 CMC 1.5 EDTA 0.2 ENZYM (protease) 0.2 Opt. Brightener 0.2 Na sulfate 10.5 Water 9.2

*) Polymer
No. 1: PAS from Example 1, VZ = 100, commercial product
No. 2: PAS, VZ = 60
No. 3: PAS from Example 2, VZ = 24
No. 4: PAS, VZ = 9
No. 5: Mixture of 50 parts PAS VZ = 100 and 50 parts PAS VZ = 60
No. 6: Mixture of 50 parts PAS VZ = 100 and 50 parts PAS VZ = 24
No. 7: Mixture of 50 parts PAS VZ = 100 and 50 parts PAS VZ = 9
No. 8: Commercial acrylic acid / maleic acid copolymer, VZ = 44

Table 3

Overall result of primary washing power (Wilcoxon-Wilcox test)

Table 5

Incrustation (loss on ignition in percent)

Claims (4)

1. Phosphate-free detergent builder, consisting of a water-insoluble, for binding calcium ions qualified silicate and a mixture of two various acrylic acid polymers, one have different viscosity numbers. 2. phosphate-free detergent builder according to claim 1, characterized in that the mixture of Acrylic acid polymers consist of two homopolymers. 3. phosphate-free detergent builder according to claim 1, characterized in that the mixture of Acrylic acid polymers from a homopolymer and a copolymer. 4. phosphate-free detergent builder according to claim 1, characterized in that the acrylic acid polymers a viscosity number from 15 to 60 and from 80 to 200 exhibit.